Herbicidal mixtures of 3-lower alkyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxides and 3,5-dibromo-4-hydroxybenzaldoxime-0-(nitrophenyl)ethers

ABSTRACT

Herbicide compositions of mixtures in the weight ratio of 5:1 to 1:5 of (a) 3-lower alkyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide or a salt thereof and (b) a compound of the formula ##SPC1## 
     Where n denotes one of the integers 1 and 2, and R denotes the radical ##SPC2##

RELATED APPLICATION

This application is a division of my copending application Ser. No. 432,676, filed Jan. 11, 1974, now abandoned which in turn is a division of my application Ser. No. 343,629, filed Mar. 22, 1973, now U.S. Pat. No. 3,888,655 the disclosure of which is incorporated herein by reference.

The present invention relates to herbicide comprising a composition of several active ingredients.

It is known that substituted phenyl ethers, carbamates, terephthalates, acid amides, benzoic acids, fluorenecarboxylic acids and benzothiadiazinones have a herbicidal action. However, this action is poor.

I have now found that a composition of

A. a compound of the formula ##SPC3##

Where R denotes lower alkyl of a maximum of 4 carbon atoms, or its salts, such as alkali metal, alkaline earth metal, ammonium, hydroxyalkylammonium, alkylammonium and hydrazine salts, e.g. salts with sodium, lithium, potassium, calcium, iron, methylammonium, trimethylammonium, ethylammonium, diethanolammonium, ethanolammonium, dimethylamine, dimethylethanolamine, hydrazine and phenylhydrazine, and

B. a compound of the formula ##SPC4##

WHERE N DENOTES ONE OF THE INTEGERS 1 AND 2 AND R denotes the radical ##SPC5##

Have a herbicidal action superior to that of their individual components.

Active ingredients a and b may be applied in amounts of 0.5 to 5 kg per hectare.

The weight ratio of a : b is from 5:1 to 1:5, preferably from 3:1 to 1:3.

The compositions of the invention are suitable for controlling unwanted plants, e.g. dicotyledonous seed weeds, monocotyledonous grassy seed weeds and Cyperaceae in crops such as cereals, rice, soybeans, Indian corn, potatoes, peas, and beans.

The compositions may be applied to the loci of the plants, pre- and/or postemergence.

The agents according to the invention may be used as solution emulsions, suspensions oil dispersions, granules or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils and oils of vegetable or mineral origin, and cyclic hydrocarbons such as tetrahydronaphthalene and alkylated naphthalenes are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e.g., polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent. Oils of various types may be added to ready-to-use spray liquors.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e.g., clay or fertilizers.

Granules may be prepared by bonding the active ingredients to solid carriers.

Directly sprayable dispersions may also be prepared with oils. The new compounds may be mixed with fertilizers, insecticides, fungicides and other herbicides.

EXAMPLE 1

The plants wheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), slender foxtail (Alopecurus myosuroides), catchweed (Galium (Galium aparine), chickweed (Stellaria media) and henbit (Lamium amplexicaule) were treated at a growth height of 4 to 20 cm with the following amounts of the following individual active ingredients and compositions thereof, each active ingredient and each composition being emulsified or dispersed in 500 liters of water per hectare:

    I    4-chlorobutyn-2-yl-1 N-3-chlorophenylcarbamate,                                     1 and 2 kg per hectare;                                              II   5-chloro-4-methyl-2-propionamide thiazole,                                          2 and 3 kg per hectare;                                              III  3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)-                     ether, 0.75 and 1.5 kg per hectare;                                       IV   9-hydroxyfluorenecarboxylic acid-(9),                                               1 and 3 kg per hectare;                                              V    3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide,                               0.75, 1.5, 2 and 3 kg per hectare;                                   I + V   1.0 + 1.0 kg per hectare;                                              II + V  2.0 + 1.0 kg per hectare;                                              III + V 0.75 + 0.75 kg per hectare;                                            IV + V  1.0 + 2.0 kg per hectare.                                         

After 8 to 12 days it was ascertained that the compositions had a better overall action than the individual active ingredients, combined with good crop plant compatibility. The results are given below:

    Active ingredient                                                                         I    II   III    IV  V               I+V II+V                                                                               III+V                  kg/ha      1  2 2  3 0.75                                                                               1.5                                                                               1 3 0.75                                                                               1  1.5                                                                               2  3  1+1 2+1 0.75+0.75              __________________________________________________________________________     Triticum aestivum                                                                         0   0                                                                               10 20                                                                                0  10  0                                                                                0                                                                               0   0   0  0  0  0  10  0                      Hordeum vulgare                                                                           0   0                                                                               10 20                                                                                5  15  0                                                                               15                                                                               0   0   0  0  0  0  10  0                      Avena fatua                                                                               70 90                                                                               50 70                                                                               --  -- --                                                                               --                                                                               5   5   5  5 10 85  80  --                     Alopecuris 60 85                                                                               50 75                                                                               --  -- --                                                                               --                                                                               5   5  10 10 15 80  80  --                     myosuroides                                                                    Galium aparine                                                                            5  10                                                                               30 45                                                                               20  45 30                                                                               85                                                                               35  40 60 70 80 80  90  90                     Stellaria media                                                                           10 30                                                                               40 65                                                                               30  70 30                                                                               90                                                                               40  60 70 90 90 90  100 100                    Lamium amplexicaule                                                                       5  10                                                                                5 10                                                                               45  80 30                                                                               95                                                                               30  40 50 60 70 75  75  100                    __________________________________________________________________________      0  = no damage                                                                 100 = complete destruction                                               

EXAMPLE 2

In the open, various plants were treated at a growth height of 3 to 25 cm with the following amounts of the following active ingredients and compositions thereof as oil dispersions:

I sodium salt of 3-isopropyl-2,1,3-benzothiadiazinone-4)-2,2-dioxide, 0.15, 0.45, 0.75 and 0.9 kg/hectare;

Ii dimethylamine salt of 3-isopropyl-2,1,3-benzothiadiazinone-(4)-dioxide, 0.15, 0.45, 0.75 and 0.9 kg/hectare;

Iii diethanolamine salt of 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, 0.15, 0.45, 0.75 and 0.9 kg/hectare;

Iv 3,5-dibromo-4-hydroxybenzaldoxim-0-(2',4'-dinitrophenyl)-ether, 0.15, 0.45, 0.75 and 0.9 kg/hectare;

V 3,5-diiodo-4-hydroxybenzonitrile, 0.15, 0.45, 0.75 and 0.9 kg/hectare;

Vi 3,5-dibromo-4-hydroxybenzonitrile, 0.15, 0.45, 0.75 and 0.9 kg/hectare;

    I + IV:  0.15 + 0.75;                                                                              0.75 + 0.15;                                                                               0.45 + 0.45 kg/ha;                             I + V:   0.15 + 0.75;                                                                              0.75 + 0.15;                                                                               0.45 + 0.45 kg/ha;                             I + VI:  0.15 + 0.75;                                                                              0.75 + 0.15;                                                                               0.45 + 0.45 kg/ha;                             II + IV: 0.15 + 0.75;                                                                              0.75 + 0.15;                                                                               0.45 + 0.45 kg/ha;                             II + V:  0.15 + 0.75;                                                                              0.75 + 0.15;                                                                               0.45 + 0.45 kg/ha;                             II + VI: 0.15 + 0.75;                                                                              0.75 + 0.15;                                                                               0.45 + 0.45 kg/ha;                             III + IV:                                                                               0.15 + 0.75;                                                                              0.75 + 0.15;                                                                               0.45 + 0.45 kg/ha;                             III + V: 0.15 + 0.75;                                                                              0.75 + 0.15;                                                                               0.45 + 0.45 kg/ha;                             III + VI:                                                                               0.15 + 0.75;                                                                              0.75 + 0.15;                                                                               0.45 + 0.45 kg/ha.                        

After 8 to 12 days it was ascertained that the compositions had a better herbicidal action than their individual components, combined with the same good crop plant compatibility.

The results are given below:

    Active ingredient                                                                         I               II              III                                 kg/ha      0.15                                                                               0.45                                                                               0.75                                                                               0.9 0.15                                                                               0.45                                                                               0.75                                                                               0.9 0.15                                                                               0.45                                                                               0.75                                                                               0.9                     __________________________________________________________________________     Crop plants:                                                                   Triticum aestivum                                                                         0    0   0   0  0   0    0   0  0    0   0   0                      Hordeum vulgare                                                                           0    0   0   0  0   0    0   0  0    0   0   0                      Secale cereale                                                                            0    0   0   0  0   0    0   0  0    0   0   0                      Unwanted plants:                                                               Galium aparine                                                                            10  30  40  55  10  26  40  47  14  28  45  60                      Lamium amplexicaule                                                                       0   10  15  23  0   9   20  35  3   10  25  32                      Stellaria media                                                                           7   18  30  42  10  26  35  45  6   20  40  50                                 IV              V               VI                                  Crop plants:                                                                   Triticum aestivum                                                                         0    0   0   0  0   10  12  15  0    5   5  10                      Hordeum vulgare                                                                           0    0   5   5  0   5    7  10  0    0   0   5                      Secale cereale                                                                            0    0   0   5  0   6   10  15  0    0   0   7                      Unwanted plants:                                                               Galium aparine                                                                            5   15  20  30  14  35  54  74  11  20  30  48                      Lamium amplexicaule                                                                       12  33  45  60  10  30  43  67  8   30  40  60                      Stellaria media                                                                           7   22  30  48  10  25  37  58  7   20  31  50                      __________________________________________________________________________

    Active ingredient                                                                         I + IV               I + V                                          kg/ha      0.15+0.75                                                                             0.75+0.15                                                                             0.45+0.45                                                                             0.15+0.75                                                                             0.75+0.15                                                                             0.45+0.45                        __________________________________________________________________________     Crop plants:                                                                   Triticum aestivum                                                                          0      0      0     12      0      0                               Hordeum vulgare                                                                            5      0      0      7      0      5                               Secale cereale                                                                             0      0      0     10      0      6                               Unwanted plants:                                                               Galium aparine                                                                            70     80     83     96     90     88                               Lamium amplexicaule                                                                       90     68     80     78     65     82                               Stellaria media                                                                           75     78     85     80     77     81                                          I + VI               II + IV                                        Crop plants:                           40                                      Triticum aestivum                                                                          5      0      5      0      0      0                               Hordeum vulgare                                                                            0      0      0      5      0      0                               Secale cereale                                                                             0      0      0                                                    Unwanted plants:                                                               Galium aparine                                                                            76     90     87     68     82     80                               Lamium amplexicaule                                                                       73     60     76     82     70     78                               Stellaria media                                                                           75     73     80     80     79     90                               __________________________________________________________________________

    Active ingredient                                                                         II + V               II + VI                                        kg/ha      0.15+0.75                                                                             0.75+0.15                                                                             0.45 +0.45                                                                            0.15+0.75                                                                             0.75+0.15                                                                             0.45+0.45                        __________________________________________________________________________     Crop plants:                                                                   Triticum aestivum                                                                         12      0     10      5      0      5                               Hordeum vulgare                                                                            7      0      5      0      0      0                               Secale cereale                                                                            10      0      6      0      0      0                               Unwanted plants:                                                               Galium aparine                                                                            97     95     93     78     90     84                               Lamium amplexicaule                                                                       80     67     75     74     66     73                               Stellaria media                                                                           85     83     92     80     85     88                                          III + IV             III+ V                                         Crop plants:                                                                   Triticum aestivum                                                                          0      0      0     12      0     10                               Hordeum vulgare                                                                            5      0      0      7      0      5                               Secale cereale                                                                             0      0      0     10      0      6                               Unwanted plants:                                                               Galium aparine                                                                            67     83     80     100    97     95                               Lamium amplexicaule                                                                       80     64     78     83     76     77                               Stellaria media                                                                           74     76     82     80     93     84                               __________________________________________________________________________

    Active ingredient                                                                           III + VI                                                          kg/ha        0.15+0.75  0.75+0.15 0.45+0.45                                    ______________________________________                                         Crop plants:                                                                   Triticum aestivum                                                                           5          0         5                                            Hordeum vulgare                                                                             0          0         0                                            Secale cereale                                                                              0          0         0                                            Unwanted plants:                                                               Galium aparine                                                                              80         92        86                                           Lamium amplexicaule                                                                         75         70        78                                           Stellaria media                                                                             72         85        79                                           ______________________________________                                          C  = no damage                                                                 100 = complete destruction                                               

EXAMPLE 3

In the greenhouse, various plants were treated at a growth height of 4 to 27 cm with the following amounts of the following individual active ingredients and compositions thereof as dispersions:

I 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, 1.0, 1.5, 2.0 and 3.0 kg/ha;

Ii 3,5-dibromo-4-hydroxybenzonitrile, 1.0, 1.5, 2.0 and 3.0 kg/ha;

Iii 3,5-diiodo-4-hydroxybenzonitrile, 1.0, 1.5, 2.0 and 3.0 kg/ha;

Iv 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)-ether, 1.0, 1.5, 2.0 and 3.0 kg/ha;

    I + II : 2.0 + 1.0; 1.0 + 2.0; 1.0 + 1.0; and 1.5 + 1.5 kg/ha;                 I + III: 2.0 + 1.0; 1.0 + 2.0; 1.0 + 1.0; and 1.5 + 1.5 kg/ha;                 I + IV : 2.0 + 1.0; 1.0 + 2.0; 1.0 + 1.0; and 1.5 + 1.5 kg/ha;            

compared with

V 1-p-chlorophenyl-3,3-dimethylurea, 2.0 and 3.0 kg/ha; and V+I: 2.0 + 1.0 kg/ha.

After 12 to 15 days it was ascertained that the compositions I + II, I + III and I + IV had a better crop plant compatibility than their individual components; active ingredients V; and composition V+I, combined with the same good herbicidal action.

The results are given below:

    Active ingredient                                                                         I               II              III                                 kg/ha      1.0 1.5 2.0 3.0 1.0 1.5 2.0 3.0 1.0 1.5 2.0 3.0                     __________________________________________________________________________     Crop plants:                                                                   Triticum aestivum                                                                          0   0   0   0  10  12  15   20 15  18  20   30                     Hordeum vulgare                                                                            0   0   0   0   5   6   8   10 10  15  18   26                     Secale cereale                                                                             0   0   0   0   8  10  14   18 17  20  25   31                     Unwanted plants:                                                               Galium aparine                                                                            40  60  70  80  50  67  90  100 75  90  98  100                     Lamium amplexicaule                                                                       40  50  60  70  60  70  85  100 70  80  94  100                     Stellaria media                                                                           60  70  90  95  54  78  90  100 60  83  97  100                     __________________________________________________________________________      0  = no damage                                                                 100 = complete destruction                                                    Active ingredient                                                                         I + II                  I + III                                     kg/ha      2.0+1.0                                                                              1.0+2.0                                                                              1.0+1.0                                                                              1.5+1.5                                                                              2.0+1.0                                                                              1.0+2.0                                                                              1.0+1.0                                                                              1.5+1.5                   __________________________________________________________________________     Crop plants:                                                                   Triticum aestivum                                                                          10    15    10    12    15    20    15    18                       Hordeum vulgare                                                                            5     8     5     6     10    18    10    15                       Secale cereale                                                                             8     14    8     10    17    25    17    20                       Unwanted plants:                                                               Galium aparine                                                                            100   100   100   100   100   100   100   100                       Lamium amplexicaule                                                                       100   100   100   100   100   100   100   100                       Stellaria media                                                                           100   100   100   100   100   100   100   100                       __________________________________________________________________________      9  = no damage                                                                 100 = complete destruction                                                    Active ingredient                                                                         IV              V                                                   kg/ha      1.0 1.5 2.0 3.0 2.0 3.0                                             __________________________________________________________________________     Crop plants:                                                                   Triticum aestivum                                                                          0  10  15   19  40  70                                             Hordeum vulgare                                                                            7  15  20   25  47  80                                             Secale cereale                                                                             6  10  12   18  56  95                                             Unwanted plants:                                                               Galium aparine                                                                            30  45  60  100  90  95                                             Lamium amplexicaule                                                                       65  80  95  100 100 100                                             Stellaria media                                                                           60  70  93  100 100 100                                             __________________________________________________________________________      0  = no damage                                                                 100 = complete destruction                                                    Active ingredient                                                                         I + IV                  I + V                                       kg/ha      2.0+1.0                                                                              1.0+2.0                                                                              1.0+1.0                                                                              1.5+1.5                                                                              1.0+2.0                                     __________________________________________________________________________     Crop plants:                                                                   Triticum aestivum                                                                          0     15    0     10    40                                         Hordeum vulgare                                                                            7     20    7     15    47                                         Secale cereale                                                                             6     12    6     10    56                                         Unwanted plants:                                                               Galium aparine                                                                            100   100   100   100   100                                         Lamium amplexicaule                                                                       100   100   100   100   100                                         Stellaria media                                                                           100   100   100   100   100                                         __________________________________________________________________________      0  = no damage                                                                 100 = complete destruction                                                

It is claimed:
 1. A herbicide composition comprising an inert carrier having dispersed therein a herbicidally effective amount of a mixture consisting essentially ofa. a compound of the formula ##SPC6##where R denotes lower alkyl of a maximum of 4 carbon atoms, or an alklai metal alkaline earth metal, ammonium, lower alkylammonium, lower hydroxyalkylammonium or hydrazine salt thereof, and b. a compound of the formula ##SPC7##where n denotes one of the integers 1 and 2, and R denotes the radical ##SPC8## in a weight ratio of a:b of 5:1 to 1:5.
 2. A herbicide composition as claimed in claim 1 wherein said weight ratio is 3:1 to 1:3 and compound (b) is 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)-ether.
 3. A process for controlling growth of unwanted plants which comprises applying to the loci of the plants a herbicide composition comprising an inert carrier having dispersed therein a herbicidally effective amount of a mixture consisting essentially ofa. a compound of the formula ##SPC9## where R denotes lower alkyl of a maximum of 4 carbon atoms, or an alkali metal, alkaline earth metal, ammonium, lower alkylammonium, lower hydroxyalkylammonium or hydrazine salt thereof and b. a compound of the formula ##SPC10## wherein n denotes one of the integers 1 and 2, and R denotes the radical ##SPC11##in a weight ratio of a:b of 5:1 to 1:5.
 4. A process as claimed in claim 3 wherein said weight ratio is 3:1 to 1:3 and compound (b) is 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)-ether.
 5. A process as claimed in claim 3 wherein said weight ratio is 3:1 to 1:3, compound (b) is 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)-ether, and compound a is 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide or said salt thereof.
 6. A process as claimed in claim 3 wherein said weight ratio is 1:1, compound (b) is 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)-ether, and compound a is 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide.
 7. A herbicide composition as claimed in claim 1 wherein said weight ratio is 3:1 to 1:3, compound (b) is 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)-ether, and compound a is 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide or said salt thereof.
 8. A herbicide composition as claimed in claim 1 wherein said weight ratio is 1:1, and compound (b) is 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)-ether, and compound a is 3-isopropyl-2,1,3-benzothiadiazonine-(4)-2,2-dioxide. 